The C-13 nuclear magnetic resonance (n.m.r.) spectra were found to pro
vide a means for direct observation of the structures formed along the
glycolide/lactide copolymer chain upon transesterification. Neverthel
ess H-1 n.m.r. spectroscopy appeared to be more convenient and useful
in the analysis of chain microstructure. The glycolide methylene group
region of the proton spectra exhibits several signals which can be as
cribed to longer sequences (as compared to those giving rise to C-13 r
esonances) as well as to the sequences which can appear only as a resu
lt of the second mode of transesterification. The analysis revealed th
at the longest blocks were in the copolymers prepared with Al(acac)(3)
as the initiator and the shortest blocks were in the copolymers obtai
ned with tin initiators. A decrease in temperature was found to reduce
the extent of the second mode of transesterification.